Bi-magnetic Mn3O4@Ni core-shell binary superparticles: Self-assembly preparation and magnetic behaviors.

Binary superparticles formed by self-assembling two different types of nanoparticles may utilize the synergistic interactions and create advanced multifunctional materials. Bi-magnetic superparticles with a core-shell structure have unique properties due to their specific spatial configurations. Herein, we built Mn3O4@Ni core-shell binary superparticles via an emulsion self-assembly technique. The superparticles are generated with a spherical morphology, and have a typical average size of about 240 nm. By altering the ratio of the two magnetic nanoparticles, the thickness of Ni shells can be adjusted. Oleic acid ligands are crucial for the formation of core-shell structure. Magnetic analysis suggests that core-shell superparticles display dual-phase magnetic interactions, contrasting with the single-phase magnetic behaviors of commonly core-shell magnetic nanoparticles. The calculation on the effective magnetic anisotropy constants indicates that the presence of Ni shell layers reduces the dipole interactions among the Mn3O4 core particles. Due to the presence of Ni nanoparticle shells, the blocking temperature of Mn3O4 is reduced, while the Curie temperature of Mn3O4 is independent on Ni content. Tunable magnetic properties can be achieved by modulating the Ni nanoparticle shell thickness. This study offers insights for the development of core-shell superparticles with varied magnetic characteristics.

An autotransferable alloy overlayer toward stable sodium metal anodes.

Sodium (Na) metal anodes receive significant attention due to their high theoretical specific energy and cost-effectiveness. However, the high reactivity of Na foil anodes and the irregular surfaces have posed challenges to the operability and reliability of Na metals in battery applications. In the absence of inert environmental protection conditions, constructing a uniform, dense, and sodiophilic Na metal anode surface is crucial for homogenizing Na deposition, but remains less-explored. Herein, we fabricated a Tin (Sn) nanoparticle-assembled film conforming to separator pores, which provided ample space for accommodating volumetric expansion during the Na alloying process. Subsequently, a seamless Na-Sn alloy overlayer was formed and transferred onto the Na foil during Na plating through a separator-assisted technique, thereby overcoming conventional operational limitations of metallic Na. As compared to traditional volumetrically expanded cracked ones, the present autotransferable, highly sodiophilic, ion-conductive, and seamless Na-Sn alloy overlayer serves as uniform nucleation sites, thereby reducing nucleation and diffusion barriers and facilitating the compact deposition of metallic Na. Consequently, the autotransferable alloy layer enables a high average Coulombic efficiency of 99.9 % at 3.0 mA cm-2 and 3.0 mAh cm-2 in the half cells as well as minimal polarization overpotentials in symmetric cells, both during prolonged cycling 1200 h. Furthermore, the assembled Na||Sn-1.0h-PP||Na3V2(PO4)3@C@CNTs full cell delivers high capacity retention of 97.5 % after 200 cycles at a high cathodic mass loading.

High-Voltage All-Solid-State Thin-Film Lithium Batteries Enabled by LiF Interlayer.

All-solid-state thin-film lithium batteries (TFBs) with high voltage are crucial for powering microelectronics systems. However, the issues of interfacial instability and poor solid contact of cathode/electrolyte films have limited their application. In this work, the preferentially orientated LiCoO2 (LCO) nanocolumns and the LCO/LiPON/Li TFBs are fabricated by in situ heating sputtering. By introducing the LiF interlayer, the solid contact of the LCO/LiPON interface is improved, enabling the high-voltage TFBs. The elemental diffusion, morphology change, and interfacial deterioration are suppressed, as demonstrated by various in situ and ex situ tests. As a result, the LCO/LiF/LiPON/Li TFB exhibits a more stable and higher capacity compared to other TFBs. This work provides guidance to improve the solid contact of TFBs and increase the performance of all-solid-state lithium batteries.

Si@Fe3O4/AC composite with interconnected carbon nano-ribbons network for high-performance lithium-ion battery anodes.

Si-based anode materials have a relatively high theoretical specific capacity and low operating voltage, greatly enhancing the energy density of rechargeable lithium-ion batteries (LIBs). However, their practical application is seriously hindered by the instability of active particles and anode electrodes caused by the huge swelling during cycling. How to maintain the stability of the charge transfer network and interface structure of Si particles is full of challenges. To address this issue, we have developed a novel Si@Fe3O4/AC/CNR anode by in-situ growing one-dimensional high elastic carbon nano-ribbons to wrap Si nanoparticles. This special structure can construct fast channels of electron transport and lithium ion diffusion, and stabilize the surface structure of Si nanoparticles during cycling. With these promising architectural features, the Si@Fe3O4/AC/CNR composite possesses a high specific capacity of 1279.4 mAh/g at 0.5 A/g, and a superior cycling life with 80 % capacity retention after 700 cycles. Even at a high current density of 20.0 A/g, the composite still delivers a capacity of 621.2 mAh/g. The facile synthetic approach and high performance of Si@Fe3O4/AC/CNR anodes provide practical insight into advanced anode materials with large volume expansion for high-energy-density LIBs.

Tailoring Li Deposition by Regulating Structural Connectivity of Electrochemical Li Reservoir in Li-metal Batteries.

Irregular Li deposition is the major reason for poor reversibility and cycle instability in Li metal batteries, even leading to safety hazards, the causes of which have been extensively explored. The structural disconnection induced by completely dissolving Li in the traditional testing protocol is a key factor accounting for irregular Li growth during the subsequent deposition process. Herein, the critical role played by the structural connectivity of electrochemical Li reservoir in subsequent Li deposition behaviors is elucidated and a morphology-performance correlation is established. The structural connection and resultant well-distributed morphology of the in situ electrochemical Li reservoir ensure efficient electron transfer and Li+ diffusion pathway, finally leading to homogenized Li nucleation and growth. Tailoring the geometry of Li reservoir can improve the coulombic efficiency and cyclability of anode-free Li metal batteries by optimizing Li deposition behavior.

Resolving the Origins of Superior Cycling Performance of Antimony Anode in Sodium-ion Batteries: A Comparison with Lithium-ion Batteries.

Alloying-type antimony (Sb) with high theoretical capacity is a promising anode candidate for both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). Given the larger radius of Na+ (1.02 Å) than Li+ (0.76 Å), it was generally believed that the Sb anode would experience even worse capacity degradation in SIBs due to more substantial volumetric variations during cycling when compared to LIBs. However, the Sb anode in SIBs unexpectedly exhibited both better electrochemical and structural stability than in LIBs, and the mechanistic reasons that underlie this performance discrepancy remain undiscovered. Here, using substantial in situ transmission electron microscopy, X-ray diffraction, and Raman techniques complemented by theoretical simulations, we explicitly reveal that compared to the lithiation/delithiation process, sodiation/desodiation process of Sb anode displays a previously unexplored two-stage alloying/dealloying mechanism with polycrystalline and amorphous phases as the intermediates featuring improved resilience to mechanical damage, contributing to superior cycling stability in SIBs. Additionally, the better mechanical properties and weaker atomic interaction of Na-Sb alloys than Li-Sb alloys favor enabling mitigated mechanical stress, accounting for enhanced structural stability as unveiled by theoretical simulations. Our finding delineates the mechanistic origins of enhanced cycling stability of Sb anode in SIBs with potential implications for other large-volume-change electrode materials.

Self-Assembled Preparation of Porous Nickel Phosphide Superparticles with Tunable Phase and Porosity for Efficient Hydrogen Evolution.

Self-assembly of colloidal nanoparticles enables the easy building of assembly units into higher-order structures and the bottom-up preparation of functional materials. Nickel phosphides represent an important group of catalysts for hydrogen evolution reaction (HER) from water splitting. In this paper, the preparation of porous nickel phosphide superparticles and their HER efficiencies are reported. Ni and Ni2P nanoparticles are self-assembled into binary superparticles via an oil-in-water emulsion method. After annealing and acid etching, the as-prepared Ni-Ni2P binary superparticles change into porous nickel phosphide superparticles. The porosity and crystalline phase of the superparticles can be tuned by adjusting the ratio of Ni and Ni2P nanoparticles. The resulting porous superparticles are effective in driving HER under acidic conditions, and the modulation of porosity and phase further optimize the electrochemical performance. The prepared Ni3P porous superparticles not only possess a significantly enhanced specific surface area compared to solid Ni-Ni2P superparticles but also exhibit an excellent HER efficiency. The calculations based on the density functional theories show that the (110) crystal facet exhibits a relatively lower Gibbs free energy of hydrogen adsorption. This work provides a self-assembly approach for the construction of porous metal phosphide nanomaterials with tunable crystalline phase and porosity.

Design principles of heterointerfacial redox chemistry for highly reversible lithium metal anode.

High electrochemical reversibility is required for the application of high-energy-density lithium (Li) metal batteries; however, inactive Li formation and SEI (solid electrolyte interface)-instability-induced electrolyte consumption cause low Coulombic efficiency (CE). The prior interfacial chemical designs in terms of alloying kinetics have been used to enhance the CE of Li metal anode; however, the role of its redox chemistry at heterointerfaces remains a mystery. Herein, the relationship between heterointerfacial redox chemistry and electrochemical transformation reversibility is investigated. It is demonstrated that the lower redox potential at heterointerface contributes to higher CE, and this enhancement in CE is primarily due to the regulation of redox chemistry to Li deposition behavior rather than the formation of SEI films. Low oxidation potential facilitates the formation of the surface with the highly electrochemical binding feature after Li stripping, and low reduction potential can maintain binding ability well during subsequent Li plating, both of which homogenize Li deposition and thus optimize CE. In particular, Mg hetero-metal with ultra-low redox potential enables Li metal anode with significantly improved CE (99.6%) and stable cycle life for 700 cycles at 3.0 mA cm-2. This work provides insight into the heterointerfacial design principle of next-generation negative electrodes for highly reversible metal batteries.

In-situ formed Co nano-clusters as separator modifier and catalyst to regulate the film-like growth of Li and promote the cycling stability of lithium metal batteries.

Lithium metal batteries (LMBs) are considered a highly prospective next-generation energy storage technology. However, their large-scale commercial application is hampered by the uncontrollable growth of Li dendrites, which accompany the boundless inflation of the battery's volume. In this study, we address this challenge by fabricating a porous structure of the MOF-derived CoP nanocube film (CoP-NC@PP) as a adorned layer for the separator. During the initial cycle, this film facilitates the in situ formation of Li3P with ultrahigh ionic conductivity and a lithiophilic Co, which helps rule the nucleation and deposition behavior of lithium and stabilizes the solid-electrolyte interphase. The symmetric cell incorporating the CoP-NC@PP modified layer exhibits exceptional cycling stability, surpassing 1500 h of continuous operation. The kinetic process of Li interaction with CoP and the structural factors contributing to the high cycling stability and high naminal voltage were investigated by molecular dynamics simulation and density functional theory calculations. Furthermore, full cells employing Li||CoP-NC@PP||LFP (LFP = LiFePO4) configurations demonstrate excellent cycling stability and high capacity, even at a high rate of 5 C (≈5.2 mA cm-2), with the cathode mass loading reaching as high as 10.3 mg cm-2.

Interlayer Confined Water Enabled Pseudocapacitive Sodium-Ion Storage in Nonaqueous Electrolyte.

Electrochemical capacitors have faced the limitations of low energy density for decades, owing to the low capacity of electric double-layer capacitance (EDLC)-type positive electrodes. In this work, we reveal the functions of interlayer confined water in iron vanadate (FeV3O8.7·nH2O) for sodium-ion storage in nonaqueous electrolyte. Using an electrochemical quartz crystal microbalance, in situ Raman, and ex situ X-ray diffraction and X-ray photoelectron spectroscopy, we demonstrate that both nonfaradaic (surficial EDLC) and faradaic (pseudocapacitance-dominated Na+ intercalation) processes are involved in the charge storages. The interlayer confined water is able to accelerate the fast Na+ intercalations and is highly stable (without the removal of water or co-intercalation of [Na-diglyme]+) in the nonaqueous environment. Furthermore, coupling the pseudocapacitive FeV3O8.7·nH2O with EDLC-type activated carbon (FeVO-AC) as the positive electrode brings comprehensive enhancements, displaying the enlarged compaction density of ∼2 times, specific capacity of ∼1.5 times, and volumetric capacity of ∼3 times compared to the AC electrode. Furthermore, the as-assembled hybrid sodium-ion capacitor, consisting of an FeVO-AC positive electrode and a mesocarbon microbeads negative electrode, shows a high energy density of 108 Wh kg-1 at 108 W kg-1 and 15.3 Wh kg-1 at 8.3 kW kg-1. Our results offer an emerging route for improving both specific and volumetric energy densities of electrochemical capacitors.

Artificial Post-Cycled Structure Modulation Towards Highly Stable Li-Rich Layered Cathode.

High-capacity Li-rich layered oxides (LLOs) suffer from severe structure degradation due to the utilization of hybrid anion- and cation-redox activity. The native post-cycled structure, composed of progressively densified defective spinel layer (DSL) and intrinsic cations mixing, is deemed as the hindrance of the rapid and reversible de/intercalation of Li+ . Herein, the artificial post-cycled structure consisting of artificial DSL and inner cations mixing is in situ constructed, which would act as a shield against the irreversible oxygen emission and undesirable transition metal migration by suppressing anion redox activity and modulating cation mixing. Eventually, the modified DSL-2% Li-rich cathode demonstrates remarkable electrochemical properties with a high discharge capacity of 187 mAh g-1 after 500 cycles at 2 C, and improved voltage stability. Even under harsh operating conditions of 50 °C, DSL-2% can provide a high discharge capacity of 168 mAh g-1 after 250 cycles at 2 C, which is much higher than that of pristine LLO (92 mAh g-1 ). Furthermore, the artificial post-cycled structure provides a novel perspective on the role of native post-cycled structure in sustaining the lattice structure of the lithium-depleted region and also provides an insightful universal design principle for highly stable intercalated materials with anionic redox activity.

Role of Substitution Elements in Enhancing the Structural Stability of Li-Rich Layered Cathodes.

Element doping/substitution has been recognized as an effective strategy to enhance the structural stability of layered cathodes. However, abundant substitution studies not only lack a clear identification of the substitution sites in the material lattice, but the rigid interpretation of the transition metal (TM)-O covalent theory is also not sufficiently convincing, resulting in the doping/substitution proposals being dragged into design blindness. In this work, taking Li1.2Ni0.2Mn0.6O2 as a prototype, the intense correlation between the "disordered degree" (Li/Ni mixing) and interface-structure stability (e.g., TM-O environment, slab/lattice, and Li+ reversibility) is revealed. Specifically, the degree of disorder induced by the Mg/Ti substitution extends in the opposite direction, conducive to sharp differences in the stability of TM-O, Li+ diffusion, and anion redox reversibility, delivering fairly distinct electrochemical performance. Based on the established paradigm of systematic characterization/analysis, the "degree of disorder" has been shown to be a powerful indicator of material modification by element substitution/doping.

Dual-Functional Lithiophilic/Sulfiphilic Binary-Metal Selenide Quantum Dots Toward High-Performance Li-S Full Batteries.

The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides (LiPSs) shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode. Herein, a bi-service host with Co-Fe binary-metal selenide quantum dots embedded in three-dimensional inverse opal structured nitrogen-doped carbon skeleton (3DIO FCSe-QDs@NC) is elaborately designed for both sulfur cathode and Li metal anode. The highly dispersed FCSe-QDs with superb adsorptive-catalytic properties can effectively immobilize the soluble LiPSs and improve diffusion-conversion kinetics to mitigate the polysulfide-shutting behaviors. Simultaneously, the 3D-ordered porous networks integrated with abundant lithophilic sites can accomplish uniform Li deposition and homogeneous Li-ion flux for suppressing the growth of dendrites. Taking advantage of these merits, the assembled Li-S full batteries with 3DIO FCSe-QDs@NC host exhibit excellent rate performance and stable cycling ability (a low decay rate of 0.014% over 2,000 cycles at 2C). Remarkably, a promising areal capacity of 8.41 mAh cm-2 can be achieved at the sulfur loading up to 8.50 mg cm-2 with an ultra-low electrolyte/sulfur ratio of 4.1 µL mg-1. This work paves the bi-serve host design from systematic experimental and theoretical analysis, which provides a viable avenue to solve the challenges of both sulfur and Li electrodes for practical Li-S full batteries.

Regulation of Interfacial Lattice Oxygen Activity by Full-Surface Modification Engineering towards Long Cycling Stability for Co-Free Li-Rich Mn-Based Cathode.

The construction of a protective layer for stabilizing anion redox reaction is the key to obtaining long cycling stability for Li-rich Mn-based cathode materials. However, the protection of the exposed surface/interface of the primary particles inside the secondary particles is usually ignored and difficult, let alone the investigation of the impact of the surface engineering of the internal primary particles on the cycling stability. In this work, an efficient method to regulate cycling stability is proposed by simply adjusting the distribution state of the boron nickel complexes coating layer. Theoretical calculation and experimental results display that the full-surface boron nickel complexes coating layer can not only passivate the activity of interface oxygen and improve its stability but also play the role of sharing voltage and protective layer to gradually activate the oxygen redox reaction during cycling. As a result, the elaborately designed cobalt-free Li-rich Mn-based cathode displays the highest discharge-specific capacity retentions of 91.1% after 400 cycles at 1 C and 94.3% even after 800 cycles at 5 C. In particular, the regulation strategy has well universality and is suitable for other high-capacity Li-rich cathode materials.

Surface-redox sodium-ion storage in anatase titanium oxide.

Sodium-ion storage technologies are promising candidates for large-scale grid systems due to the abundance and low cost of sodium. However, compared to well-understood lithium-ion storage mechanisms, sodium-ion storage remains relatively unexplored. Herein, we systematically determine the sodium-ion storage properties of anatase titanium dioxide (TiO2(A)). During the initial sodiation process, a thin surface layer (~3 to 5 nm) of crystalline TiO2(A) becomes amorphous but still undergoes Ti4+/Ti3+ redox reactions. A model explaining the role of the amorphous layer and the dependence of the specific capacity on the size of TiO2(A) nanoparticles is proposed. Amorphous nanoparticles of ~10 nm seem to be optimum in terms of achieving high specific capacity, on the order of 200 mAh g-1, at high charge/discharge rates. Kinetic studies of TiO2(A) nanoparticles indicate that sodium-ion storage is due to a surface-redox mechanism that is not dependent on nanoparticle size in contrast to the lithiation of TiO2(A) which is a diffusion-limited intercalation process. The surface-redox properties of TiO2(A) result in excellent rate capability, cycling stability and low overpotentials. Moreover, tailoring the surface-redox mechanism enables thick electrodes of TiO2(A) to retain high rate properties, and represents a promising direction for high-power sodium-ion storage.

Stainless Steel-Like Passivation Inspires Persistent Silicon Anodes for Lithium-Ion Batteries.

Passivation of stainless steel by additives forming mass-transport blocking layers is widely practiced, where Cr element is added into bulk Fe-C forming the Cr2 O3 -rich protective layer. Here we extend the long-practiced passivation concept to Si anodes for lithium-ion batteries, incorporating the passivator of LiF/Li2 CO3 into bulk Si. The passivation mechanism is studied by various ex situ characterizations, redox peak contour maps, thickness evolution tests, and finite element simulations. The results demonstrate that the passivation can enhance the (de)lithiation of Li-Si alloys, induce the formation of F-rich solid electrolyte interphase, stabilize the Si/LiF/Li2 CO3 composite, and mitigate the volume change of Si anodes upon cycling. The 3D passivated Si anode can fully retain a high capacity of 3701 mAh g-1 after 1500 cycles and tolerate high rates up to 50C. This work provides insight into how to construct durable Si anodes through effective passivation.

Boosting the potassium-ion storage performance enabled by engineering of hierarchical MoSSe nanosheets modified with carbon on porous carbon sphere.

Developing suitable electrode materials capable of tolerating severe structural deformation and overcoming sluggish reaction kinetics resulting from the large radius of potassium ion (K+) insertion is critical for practical applications of potassium-ion batteries (PIBs). Herein, a superior anode material featuring an intriguing hierarchical structure where assembled MoSSe nanosheets are tightly anchored on a highly porous micron-sized carbon sphere and encapsulated within a thin carbon layer (denoted as Cs@MoSSe@C) is reported, which can significantly boost the performance of PIBs. The assembled MoSSe nanosheets with expanded interlayer spacing and rich anion vacancy can facilitate the intercalation/deintercalation of K+ and guarantee abundant active sites together with a low K+ diffusion barrier. Meanwhile, the thin carbon protective layer and the highly porous carbon sphere matrix can alleviate the volume expansion and enhance the charge transport within the composite. Under these merits, the as-prepared Cs@MoSSe@C anode exhibits a high reversible capacity (431.8 mAh g-1 at 0.05 A g-1), good rate capability (161 mAh g-1 at 5 A g-1), and superior cyclic performance (70.5% capacity retention after 600 cycles at 1 A g-1), outperforming most existing Mo-based S/Se anodes. The underlying mechanisms and origins of superior performance are elucidated by a set of correlated in-situ/ex-situ characterizations and theoretical calculations. Further, a PIB full cell based on Cs@MoSSe@C anode also exhibits an impressive electrochemical performance. This work provides some insights into developing high-performance PIBs anodes with transition-metal chalcogenides.

Adjustable Mixed Conductive Interphase for Dendrite-Free Lithium Metal Batteries.

Lithium (Li) metal batteries with high energy density are of great promise for next-generation energy storage; however, they suffer from severe Li dendritic growth and an unstable solid electrolyte interphase. In this study, a mixed ionic and electronic conductive (MIEC) interphase layer with an adjustable ratio assembled by ZnO and Zn nanoparticles is developed. During the initial cycle, the in situ formed Li2O with high ionic conductivity and a lithiophilic LiZn alloy with high electronic conductivity enable fast Li+ transportation in the interlayer and charge transfer at the ion/electron conductive junction, respectively. The optimized interface kinetics is achieved by balancing the ion migration and charge transfer in the MIEC Li2O-LiZn interphase. As a result, the symmetric cell with MIEC interphase delivers superior cycling stability of over 1200 h. Also, Li||Zn-ZnO@PP||LFP (LFP = LiFePO4) full cells exhibit long cyclic life for 2000 cycles with a very high capacity retention of 91.5% at a high rate of 5 C and stable cycling for 350 cycles at a high LFP loading mass of 13.27 mg cm-2.

In Situ Induced Lattice-Matched Interfacial Oxygen-Passivation-Layer Endowing Li-Rich and Mn-Based Cathodes with Ultralong Life.

The high capacity of Li-rich and Mn-based (LRM) cathode materials is originally due to the unique hybrid anion- and cation redox, which also induces detrimental oxygen escape. Furthermore, the counter diffusion of released oxygen (into electrolyte) and induced oxygen vacancies (into the interior bulk phase) that occurs at the interface will cause uncontrolled phase collapse and other issues. Therefore, due to its higher working voltage (>4.7 V) than the activation voltage of lattice oxygen in LRM (≈4.5 V), the anion-redox-free and structurally consistent cobalt-free LiNi0.5 Mn1.5 O4 (LNMO) is selected to in situ construct a robust, crystal-dense and lattice-matched oxygen-passivation-layer (OPL) on the surface of LRM particles by the electrochemical delithiation to protect the core layered components. As expected, the modified sample displays continuously decreasing interfacial impedance and high specific capacity of 135.5 mAh g-1 with a very small voltage decay of 0.67 mV per cycle after 1000 cycles at 2 C rate. Moreover, the stress accumulation during cycling is mitigated effectively. This semicoherent OPL strengthens the surface stability and interrupts the counter diffusion of oxygen and oxygen vacancies in LRM cathode materials, which would provide guidance for designing high-energy-density layered cathode materials.

Enhanced Cyclability of Lithium Metal Anodes Enabled by Anti-aggregation of Lithiophilic Seeds.

Constructing 3D skeletons modified with lithiophilic seeds has proven effective in achieving dendrite-free lithium metal anodes. However, these lithiophilic seeds are mostly alloy- or conversion-type materials, and they tend to aggregate and redistribute during cycling, resulting in the failure of regulating Li deposition. Herein, we address this crucial but long-neglected issue by using intercalation-type lithiophilic seeds, which enable antiaggregation owing to their negligible volume expansion and high electrochemical stability against Li. To exemplify this, a 3D carbon-based host is built, in which ultrafine TiO2 seeds are uniformly embedded in nitrogen-doped hollow porous carbon spheres (N-HPCSs). The TiO2@N-HPCSs electrode exhibits superior Coulombic efficiency, high-rate capability, and long-term stability when evaluated as compertitive anodes for Li metal batteries. Furthermore, the superiority of intercalation-type seeds is comprehensively revealed through controlled experiments by various in situ/ex situ electron and optical microscopies, which highlights the excellent structural stability and lithiophilicity of TiO2 nanoseeds upon repeated cycling.